AU9238998A - Non-silking iron oxide yellow pigments with high colour density - Google Patents
Non-silking iron oxide yellow pigments with high colour density Download PDFInfo
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- AU9238998A AU9238998A AU92389/98A AU9238998A AU9238998A AU 9238998 A AU9238998 A AU 9238998A AU 92389/98 A AU92389/98 A AU 92389/98A AU 9238998 A AU9238998 A AU 9238998A AU 9238998 A AU9238998 A AU 9238998A
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- AU
- Australia
- Prior art keywords
- iron oxide
- oxide yellow
- yellow pigments
- lacquer
- pigment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims description 52
- 239000001052 yellow pigment Substances 0.000 title claims description 27
- 239000000049 pigment Substances 0.000 claims description 70
- 239000004922 lacquer Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 21
- 229910002588 FeOOH Inorganic materials 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 16
- 239000004033 plastic Substances 0.000 claims description 13
- 229920003023 plastic Polymers 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000003973 paint Substances 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000001034 iron oxide pigment Substances 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 239000000243 solution Substances 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 235000011121 sodium hydroxide Nutrition 0.000 description 15
- 238000005259 measurement Methods 0.000 description 12
- 239000005569 Iron sulphate Substances 0.000 description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000005273 aeration Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 235000013980 iron oxide Nutrition 0.000 description 9
- 238000003801 milling Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 7
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000011164 primary particle Substances 0.000 description 7
- 229920000180 alkyd Polymers 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000001164 aluminium sulphate Substances 0.000 description 3
- 235000011128 aluminium sulphate Nutrition 0.000 description 3
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- -1 aromatic nitro compounds Chemical class 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000011023 white opal Substances 0.000 description 2
- 239000002478 γ-tocopherol Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000289659 Erinaceidae Species 0.000 description 1
- 241000231392 Gymnosiphon Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- VFGRALUHHHDIQI-UHFFFAOYSA-N butyl 2-hydroxyacetate Chemical compound CCCCOC(=O)CO VFGRALUHHHDIQI-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- WHIVNJATOVLWBW-SNAWJCMRSA-N methylethyl ketone oxime Chemical compound CC\C(C)=N\O WHIVNJATOVLWBW-SNAWJCMRSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/22—Compounds of iron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compounds Of Iron (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Our Ref: 707759 P/00/011 Regulation 3:2
AUSTRALIA
Patents Act 1990
ORIGINAL
COMPLETE SPECIFICATION STANDARD PATENT Applicant(s): Bayer Aktiengesellschaft D-51368 Leverkusen
GERMANY
Address for Service: Invention Title: DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 Non-silking iron oxide yellow pigments with high colour density The following statement is a full description of this invention, including the best method of performing it known to me:- 5020 Le A 32 688-Foreign Countries F/ngb/NT -1- Non-silkingiron oxide yellow pigments with high colour density The present patent application relates to iron oxide yellow pigments in the a-FeOOH modification with a low silking index which have a high yellow index a process for their preparation and their use.
Yellow iron oxide pigments in the a-FeOOH modification can be prepared by precipitation processes from Fe(II)-salt solutions followed by oxidation with air or other oxidising agents or by the so called Penniman-Zoph process in the presence of metallic iron and simultaneous oxidation with air or by oxidation of metallic iron with other oxidising agents, in particular with aromatic nitro compounds.
The yellow iron oxides prepared in this way are mainly used as pigments in lacquers and paints, building materials or for colouring plastic materials.
The colouring properties of yellow iron oxide pigments are substantially determined by the particle size, particle shape, particle size distribution and by the state of agglomeration. o-FeOOH particles which have been prepared by the processes mentioned above generally crystallise in a very definite needle shape. The scattering and absorption coefficients perpendicular and parallel to the needle axis differ considerably. If the needles are first arranged perpendicular and then parallel to the direction of observation, considerable colour differences are visible to the observer.
This effect is called the silking effect because it can also be observed on silk fabrics.
With reference to iron oxide pigments the silking effect is a particular nuisance in the case of lacquers which are applied in one direction (so-called image framework effect) and as a result of the alignment of pigments during the extrusion and calendering of plastics and plastic foils.
Patent DE-C 33 26 632 describes processes for preparing iron oxide yellow pigments with a low silking effect. The pigments described there are prepared in such a way Le A 32 688-Foreign Countries -2that the production of seeds takes place in the presence of compounds of the elements B, Al, Ga, Si, Ge, Sn or Pb, in particular in the presence of silicates or aluminates, in amounts of 0.05 to 10 calculated as the 3- or 4-valent oxides and with respect to the a-FeOOH precipitated during seed production, and an iron oxide yellow pigment can be grown onto the yellow seed prepared in this way in a conventional manner. Relating to the process of pigment growth in DE-C 33 26 632 reference is made to the prior art. The patent examples show that precipitation is performed at a constant pH of 4.0 0.1 and that the growth takes place relatively rapidly so that reproduction factors of 7 to 14 are achieved after 12 to 25 hours. The pigments are characterised in that they have a very low silking effect and in a colour test in a lacquer based on ®Alkydal F48 (medium-oil alkyd resin lacquer; Bayer AG) at a pigment/volume concentration of 10 the limits for L* are between 52 and 63, for a* are between 8 and 14 and for b* are between 40 and 48, on the CIELAB colour coordinates. Elimination of the silking effect is achieved in that highly dendritic needles are produced which grow together to give spherical aggregates (like little "hedgehogs"). These approximately isometric aggregates can no longer be aligned in specific preferred directions.
The disadvantage of the pigments prepared in accordance with DE-C 33 26 632 is that they are sensitive to milling and on the other hand do not quite achieve peak values for the yellow index b* which is obtained by some light yellow iron oxide pigments with a silking effect.
The object was therefore to prepare non-silking iron oxide yellow pigments which are relatively insensitive to milling and have a high yellow index b*.
Surprisingly, the desired pigment can be prepared by starting from the same seeds described in DE-C 33 26 632 which are built up in the process of pigment growth to completely dendrite-free primary particles. These primary particles are agglomerated to packages, where several particles lie side by side. The primary particles themselves have only a very low tendency to be needle shaped. Technically, the Le A 32 688-Foreign Countries -3modified primary particles and agglomerated structure are achieved by building up the pigment at pH values less than 3.9, preferably less than 3.8 and at the same time by building up the pigments very slowly.
The invention provides a process for preparing iron oxide yellow pigments in the c-FeOOH modification in which a) x-FeOOH seeds are produced by precipitation from an Fe(II)-containing solution using an alkaline precipitating agent in the presence of soluble aluminium salts in an amount of 3 to 9 calculated as A1 2 0 3 with respect to precipitated c-FeOOH, and subsequent oxidation to give c-FeOOH and b) the pigment is produced by precipitating further iron with simultaneous oxidation, wherein the seed/time yield is less 0.3 preferably less than 0.2hW', and the pH over the entire period of pigment growth is less than 3.9, preferably less than 3.8 and c) pigment growth is terminated at a reproduction factor between 3 and Thus, in the first process step, a-FeOOH seeds are prepared by initially introducing an Fe(II) salt solution, preferably an FeSO 4 solution, and an aluminium salt solution, preferably an aluminium sulphate solution, this mixture is heated to the desired seed production temperature which can vary between room temperature and 80'C, then part of the iron ions are precipitated using an alkaline precipitating agent, with stirring, wherein alkali metal and alkaline earth metal oxides, hydroxides or carbonates and ammonia may be mentioned as precipitating agents, and then the precipitated product is oxidised to cx-FeOOH using air or other oxidising agents. The A1 2 0 3 concentration is between 3 and 9 with respect to the x-FeOOH produced.
Le A 32 688-Foreign Countries -4- In the second process step, these seeds grow via a precipitation and oxidation process to give pigments by adding further iron(II) salt solution and converting the iron(II) to ct-FeOOH by controlled addition of precipitating agent and simultaneous oxidation.
In order to be able to obtain pigments according to the invention, it must be ensured that the pH value during the entire pigment production step is less than 3.9, preferably less than 3.8 and at the same time that pigment growth is performed very slowly. The concentration-independent quantity, the so-called seed/time yield has proven useful for characterising the rate of pigment growth. This is defined as: Amount of pigment produced Seed/time yield Seed/time yield Amount of seed used x pigment growth period RF-1 Pigment growth period The so-called reproduction factor (RF) is the ratio of total amount of pigment amount of seed amount of pigment produced) to amount of seed.
In order to prepare pigments according to the invention, a seed/time yield of less than 0.3 hW, preferably less than 0.1 is required. The seed/time yield can be controlled by the pH value and the rate of aeration.
The seeds are built up to reproduction factors between 3 and 20, depending on whether the pigment is intended to be used as a pure shade or for lightening. Highly built-up pigments with a reproduction factor between 8 and 20 are characterised by a particularly high CIELAB index b* when used as a pure shade. These types of iron oxide yellow pigments have colour indices in the CIELAB colour coordinates, in a pure shade with a pigment/volume concentration of 10 in a test lacquer, of a* between 8 and 14, b* between 48.5 and 52 and L* between 54 and 62.
Le A 32 688-Foreign Countries Less highly built-up pigments with a reproduction factor between 3 and 8 are characterised by a particularly high CIELAB index b* for lightening. These types of iron oxide yellow pigments have colour indices on the CIELAB colour coordinates for lightening with a titanium oxide pigment in the ratio 1:5, at a pigment/volume concentration of 10 in the test lacquer, of a* between 3 and 7 and b* between 38 and 41.
Electron microscope photographs show that the primary particles, in contrast to the processes known hitherto, have only a weakly expressed needle shape, are completely free of dendrites and are agglomerated to packages where the primary particles lie side by side. The yellow index b* of the pigments is modified only very slightly during milling.
Pigments according to the invention are all characterised by a low silking index of less than 5, preferably less than 3, in particular less than 1.
Furthermore, the pigments according to the invention are characterised by a low binder requirement during the preparation of lacquers. This can be characterised by oil absorption indices of less than 40 g/ 100 g.
Due to their properties, the pigments according to the invention are particularly suitable for preparing lacquers and paints and for colouring plastic materials. Use of the pigments according to the invention for colouring lacquers, paints or plastic materials is therefore also an object of the invention.
The parts and percentages quoted in the following examples refer to weight unless stated otherwise.
Le A 32 688-Foreign Countries -6- 1. Silking Index The so-called silking index is defined as a standard, independent quantity for measuring the silking effect. The silking index is measured and calculated using the following methods: 1.1 Preparation in an alkyd resin paste to measure the silking index The pigment is prepared using an automatic muller in a non-drying test binder. The test binder (paste) consists of two components: Component 1: Component 1 is an alkyd resin binder based on linseed oil and phthalic anhydride. It corresponds to the specifications which are mentioned in the standards DIN EN ISO 787-24:1995, ISO 787-25:1993 and DIN 55 983 (1983) as specifications for a test binder for coloured pigments. The product ®Sacolyd L 640 (Krems Chemie, formerly ®Alkydal L 64, Bayer AG) is used.
Component 2: Component 2 is a rheological additive which is added to make the paste thixotropic.
A powdered, modified, hydrogenated castor oil, ®LUVOTHIX HT (Lehmann Voss Co) is used at a concentration of 5.0 The Luvothix HT is dissolved in the Sacolyd L 640 at 75 to 95°C. The cooled, spreadable material is passed once through a triple-roll mill. The paste is then ready for use.
An automatic muller is used to prepare the pigment paste, as described in DIN EN ISO 8780-5 (1995). An ®ENGELSMANN JEL 25/53 muller with an effective plate diameter of 24 cm is used. The speed of rotation of the lower plate is about 75 min'.
By suspending a 2.5 kg loading weight on the loading attachment, the force between Le A 32 688-Foreign Countries -7the plates is adjusted to about 0.5 kN. 0.40 g of pigment and 5.00 g of paste are dispersed in three stages of 25 revolutions each in accordance with the method described in DIN EN ISO 8780-5 (1995) section 8.1.
Then the pigment/paste mixture is painted onto a paste film holder which corresponds in function to the paste film holder in DIN 55983 (December 1983). The doctor blade associated with the paste holder is drawn over the depression in the holder filled with the pigment paste mixture so that a smooth surface is produced.
The doctor blade is moved in one direction at a speed of about 3 to 7 cm/s. Any needle-shaped particles present in the paste are then aligned in the direction of spreading. The sample is measured within a few minutes.
1.2 Instrument for measuring the silking index.
The measuring geometry 8/d used for silking measurement is described in ISO 7724/2-1984 point 4.1.1, in DIN 5033 part 7 (1983) point 3.2.4 and in DIN 53 236 (January 1983) point 7.1.1. A ®PERKIN ELMER LAMBDA 19 spectrophotometer with a "LABSPHERE integrating sphere of 15 cm diameter is used.
A commercially available polarizing filter of adequate size is placed outside the integrating sphere, in the illuminating beam for the sample port, in a defined position for measurement, so that the direction of the electric field Vector E of the transmitted light beam is known at the sample port. The filter has a degree of polarizing 99 The reference beam remains unchanged without a filter.
The reference port in the integrating sphere is covered with a diffuse scattering white opal glass standard. A gloss trap is not used.
A further white opal glass standard (working standard) is mounted at the sample port and the instrument is calibrated. The working standard complies with the specifications described in ISO 7724/2-1984 section 8.3. The reflectance data for Le A 32 688-Foreign Countries -8the working standard against a perfect reflecting diffuser are stored in the computer so that all color measurements are given with respect to the perfect reflecting diffuser after calibration with the white working standard. The dark current at the zero point is measured with a black-cavity light trap, stored in the computer and taken into account by the measurement programme during calibration.
1.3 Measurement and calculation of the silking index.
Measurement takes place immediately after preparation of the test specimen. The temperature of the spectrophotometer and sample is about 25°C The sample is measured in two positions at right angles to each other with reference to the polarizing filter: Measurement Y1: Measurement Y2: The pigment particles are directed with their longest axes largely parallel to the electric field vector of the illuminating beam. The spreading direction on the paste film holder is parallel to the electric field vector.
The pigment particles are aligned with their longest axes largely perpendicular to the electric field vector of the illuminating beam. The spreading direction on the paste film holder and the electric field vector are perpendicular to each other.
A device for rotating the sample through 90' is useful but not absolutely necessary if appropriate markings are applied at the sample port.
The tristimulus value Y is calculated from the measured reflectance spectra in accordance with the calculation instructions in ASTM E 308 1985, point 7. The 1931 weighting functions for Standard Illuminant C and the 2' Standard Observer are Le A 32 688-Foreign Countries -9used in Table 5.6. The wavelength range is between 400 nm and 700 nm. The wavelength interval is 20 nm. The specular Component is included in the calculations.
The silking index SI is then calculated as follows from the tristimulus value Y: SI= (1 Y1/Y2-) x 100 The results are rounded to the nearest whole number.
2. CIELAB color coordinates 2.1 Preparation in an alkyd resin lacquer for measuring the mass tone (full shade).
The pigment is dispersed in an air-drying lacquer system using a muller. The lacquer system consists of the following components: 95.26 0.78 1.30% ®ALKYDAL F 48 (binder, Bayer AG, medium-oil, air-drying alkyd resin based on drying plant fatty acids in white spirit/xylene mixture 38:7 with a non-volatile fraction of about 55 oil content/triglyceride in the non-volatile fraction about 48 phthalic anhydride in the non-volatile fraction about 26 2-butanone oxime, 55 strength in white spirit (skin-preventing agent) ®Octa Soligen calcium (wetting agent, calcium salt of branched C 6
-C
1 9 fatty acids in a hydrocarbon mixture (contains 4 Ca), Borchers AG) Le A 32 688-Foreign Countries 0.22 "Octa Soligen cobalt 6 (drying agent, cobalt salt of branched
C
6
-C
1 9 fatty acids in a hydrocarbon mixture (contains 6% cobalt), Borchers AG) 0.87 ®Octa Soligen zirconium 6 (drying agent, zirconium salt of branched
C
6
-C
1 9 fatty acids in a hydrocarbon mixture (contains 6 Zr), Borchers AG) 1.57 n-butyl glycolate butyl ester of hydroxyacetic acid) (levelling agent) The components are mixed with a high speed stirrer to give the final lacquer. A muller as described in DIN EN ISO 8780-5 (April 1995) is used. An ®ENGELSMANN JEL 25/53 muller with an effective plate diameter of 24 cm is used. The speed of rotation of the lower plate is about 75 min'. By suspending a kg loading weight on the loading attachment, the force between the plates is adjusted to about 0.5 kN. 0.80 g of pigment and 2.00 g of lacquer are dispersed in one step at 100 revolutions with 2.5 kg loading weight according to the process described in DIN EN ISO 8780-5 (April 1995) section 8.1. The Muller is opened and the lacquer is rapidly collected in the lower plate away from the mid-point. Then a further 2.00 g of lacquer are added and the plates clamped together. After two stages at 50 rotations without a loading weight, preparation is terminated.
The pigmented lacquer is painted with a film applicator (clearance at least 150 pm, at most 250 m) onto a non-absorbable white paper. The lacquered chart is then dried for at least 12 hours at room temperature. Prior to the colour measurement the chart is dried at about 65°C 5oC) for 1 hour and then cooled.
Le A 32 688-Foreign Countries 11 2.2 Preparation in an alkyd resin lacquer for measuring the reduction.
The pigment and the lightening pigment are dispersed using a muller in an air-drying lacquer system. As lightener, a commercially available ®Bayertitan R-KB-2 titanium dioxide pigment (Bayer AG) is used. This pigment corresponds to type R 2 in ISO 591 1977. The lacquer system corresponds to that described under item 2.1.
The components of the lacquer system are mixed in a high speed stirrer to give the final lacquer.
The pigmented lacquer is prepared and the lacquered chart is produced in the same way as described under 2.1, wherein 0.1500 g of the pigment being tested, 0.7500 g of ®Bayertitan R-KB-2 titanium dioxide pigment and 2 x 2.00 g of lacquer are weighed out.
2.3 Spectrophotometer A spectrophotometer with an integrating sphere and with the measuring geometry d/8 without a gloss trap is used. This measuring geometry is described in ISO 7724/2 1984 point 4.1.1, in DIN 5033 part 7 (July 1983) point 3.2.4 and in DIN 53236 (January 1983) point 7.1.1. A ®Dataflash 2000 instrument from the Datacolor International Co. is used.
The spectrophotometer is calibrated with a white, ceramic working standard, as described in ISO 7724/2-1984(E) point 8.3. The reflectance data for the working standard are compared against a perfect reflecting diffuser in the colouring measuring instrument so that after calibration with the white working standard all color measurements are given with reference to the perfect reflecting diffuser. Zero point calibration is carried out using a black-cavity light trap from the spectrophotometers manufacturer.
Le A 32 688-Foreign Countries -12- 2.4 Color measurement No gloss trap is used. The temperature of the spectrophotometer and the specimen is about 25C The lacquer chart prepared in accordance with 2.1 or 2.2 is mounted onto the sample port of the spectrophotometer so that the sample port covers a central location on the painted layer. The sample must lie flat without any gap between chart and sample port. The measuring opening must be covered completely by the lacquer layer.
Measurement then takes place.
Calculating the CIE coordinates The 1976 CIE coordinates a* and b* are calculated from the measured reflectance spectrum in accordance with the calculation instructions in ASTME 308 1985, point 7. The weighting functions for standard illuminant C and the 1931 2' standard observer in ASTM E 308 1985, table 5.6 are used. The wavelength range is between 400 nm and 700 rnm. The wavelength interval is 20 nm. The specular component is included in the calculations.
Le A 32 688-Foreign Countries -13- Examples The invention is described in the following by way of examples, without this being regarded as a restriction.
Example 1 8 1 of a technical grade iron sulphate solution with a concentration of 170 g/l is placed in a glass container. 321 g of an A1 2
(SO
4 3 solution containing 7.54 wt.% calculated as A1 2 0 3 is added thereto. The solution is heated to 40'C while nitrogen gas is passed through it. The pH is adjusted to 3.5 by adding NaOH. Then with further aeration with nitrogen and stirring, 1056 ml of caustic soda solution with a concentration of 344 g of NaOH1 are added over the course of 20 min. When precipitation has finished, the mixture is aerated with air at 150 I/h, with stirring, at 40'C. When the pH has dropped to 3.6, seed formation is terminated.
In order to produce the pigment, 4196 ml of the seed suspension of nuclei mentioned above, 1235 ml of iron sulphate solution with an FeSO 4 concentration of 231.4 g/l and 569 ml of water are heated to 75°C, with stirring, in a glass container. Then pigment growth is started by simultaneously controlling the addition of caustic soda solution and aeration with air so that the pH is held between 3.5 and 3.7. Each time the iron sulphate concentration drops below a value of 5 g/l, a further batch of iron sulphate solution is added so that the concentration after topping up increases again to 30 g/l. After an oxidising time of 204 h, a sample is taken out, filtered, washed, dried, deagglomerated milling in a micro-dismembrator (Braun AG) for 8 sec and analysed. The reproduction factor is 17.1. The seed/time yield calculated is 0.08 hl.
The data on colour evaluation are given in table 1. In addition to the absolute colour indices the difference colour indices as compared with the type ®Bayferrox 920 (Bayer AG) are also given. The aluminium content of the pigment is 0.14 Le A 32 688-Foreign Countries -14- Example 2 Same as example 1, but using pure iron sulphate solution. After an oxidising time of 164 h, a sample is taken out, filtered, washed, dried and deagglomerated. The reproduction factor is 15.8. The seed/time yield calculated is 0.09 h 1 The data for colour evaluation are given in table 1.
Example 3 Same as example 2, but the sample is taken after an oxidising time of 184 h. The reproduction factor is 17.7. The seed/time yield calculated is 0.09h'. On a transmission electron microscope photograph, only short needled particles can be detected which are agglomerated to packages of several primary particles. The sample was milled with 10 mm agate spheres for 60 sec. respectively 120 sec. in a micro-dismembrator (Braun Co.) during incorporation into a lacquer to test for sensitivity to milling. The data for colour evaluation are given in table 1. The difference colour indices as compared with Bayferrox 920 are also cited alongside the absolute colour indices. The aluminium content of the pigment is 0.15 Example 4 8 1 of a technical grade iron sulphate solution with a concentration of 170 g/l are placed in a glass container. 321 g of an A1 2
(SO
4 3 solution, containing 7.54 wt.% calculated as A1 2 0 3 are added. The solution is heated to 40 0 C while nitrogen is passed through it. The pH is adjusted to 3.5 by adding NaOH. Then 1124 ml of caustic soda solution with a concentration of 323 g NaOH/I1 are added over the course of 20 min with further aeration with nitrogen and stirring. After completion of precipitation, the mixture is aerated with 150 I/h of air at 40 0 C with further stirring.
When the pH has dropped to 3.5, seed production is terminated.
Le A 32 688-Foreign Countries To build up the pigment, 4358 ml of the seed suspension of nuclei mentioned above, 1301 ml of iron sulphate solution, with an FeSO 4 content of 210 g/l, and 341 ml of water are heated to 75C, with stirring, in a glass container. Pigment production is started by simultaneous control of the addition of caustic soda solution and aeration with air, so that the pH is held between 3.2 and 3.8. Each time the iron sulphate content drops to a value below 10 g/l, a batch of 2857 ml of iron sulphate solution is added. After an oxidising time of 45 h a sample is removed, filtered, washed, dried, deagglomerated by 8 sec milling in a micro-dismembrator (Braun Co.) and analysed.
The reproduction factor is 6.2. The nucleus/time yield calculated is 0.12 h The sample was tested for lightening. The colour evaluation data are given in table 1.
Comparison Example 1 (in accordance with DE-C 33 26 632, Example 4) 250 ml of aluminium sulphate solution which contains 117 g of A1 2 (S0 4 3 .18H 2 0 are added to 15309 ml of an iron sulphate solution with an FeSO 4 content of 200 g/1. The solution is heated to 55°C. Then 2506 ml of NaOH solution with an NaOH content of 323 g/l are added over the course of 20 min, with stirring and aeration with nitrogen and then the mixture is aerated with 400 1/h of air. Seed production is terminated when the pH value reaches 2.8.
2777 ml of the seed suspension mentioned above and 7129 ml of water are heated to 0 C with the passage of nitrogen. With simultaneous aeration using 1000 1/h of air and pH-controlled addition of caustic soda solution with a concentration of 190 g/1 of NaOH, 10.75 1 of FeSO 4 solution with a concentration of 200 g/l of FeSO 4 are added dropwise over the course of 12 h so that the pH remains constant at 4.0 0.1. The pigment produced is filtered, washed, dried and deagglomerated. The reproduction factor is 11.1. The seed/time yield calculated is 0.84 h The colour evaluation data are given in table 1. The difference colour values compared with Bayferrox 920 are also cited alongside the absolute colour values.
Le A 32 688-Foreign Countries -16- Comparison Example 2 (in accordance with DE-C 33 26 632, Example 7) 400 ml of aluminium sulphate solution which contains 351 g of Al 2 (SO4) 3 .18H 2 0 are added to 15309 ml of an iron sulphate solution with an FeSO 4 concentration of 200 g/1. The solution is heated to 55°C. Then, with stirring and aeration with nitrogen, 2506 ml of NaOH solution with an NaOH concentration of 323 g/1 are added over the course of 20 min and then the mixture is aerated with 400 1/h of air.
Seed production is completed when the pH reaches 2.8.
2978 ml of the seed suspension mentioned above and 7022 ml of water are heated to aeration with nitrogen. With simultaneous aeration using 1000 1/h of air and pH-controlled addition of caustic soda solution with a concentration of 190 g/1 of NaOH, 7 1 of FeSO 4 solution with a concentration of 200 g/l of FeSO 4 are added dropwise over the course of 13 h so that the pH remains constant at 4.0 0.1. The pigment produced is filtered, washed, dried and deagglomerated. The reproduction factor is 7.2. The nucleus/time yield calculated is 0.48 The sample is milled in a micro-dismembrator (Braun using 10 mm agate spheres, for 60 sec. or 120 sec.
in order to test the sensitivity to milling during incorporation into a lacquer. The colour evaluation data are given in table 1. The difference colour indices compared with Bayferrox 920 are given in addition to the absolute colour indices.
Table 1: Colour evaluations of samples from examples 1 to 6 Example Milling Silking Pure shade or a* b* L* da* against db* against dL* against index lightening Bayferrox 920 Bayferrox 920 Bayferrox 920 1 8 sec 0.8 Pure shade 12 49.3 59 1.2 2.9 2 8 sec 0.6 Pure shade 12 48.8 58.2 1.2 2.4 -1.3 3 8 sec 0.8 Pure shade 12.1 48.8 58.1 1.3 2.4 -1.4 sec 1.9 Pure shade 11.3 48.8 59.4 0.3 2.6 0.1 120 sec 2.5 Pure shade 11 48.6 59.8 0 2.4 4 8 sec 1.5 Lightening 4.1 39 82.1 -0.3 4.7 4.7 8 sec 3.5 Pure shade 11 43.7 58.3 0.1 -2.6 -1 6 8 sec 1.4 Pure shade 12.7 45.1 56 1.9 -1.3 sec 1.6 Pure shade 12.3 44.6 56.2 1.5 -1.8 -3.3 120 sec 1.8 Pure shade 12.2 44.1 56.2 1.4 -2.3 -3.3 Comment on example 3 respectively 6: The pigment wich was prepared in example 3 was milled with the lacquer for different times (8s, 120s respectively 160s). These different lacquer preparations have different colors and coloristic values which are shown in the table. Example 3 demonstrates that pigment of example 3 is quite less sensitive to milling than comparative example 6 according to b*.
-12/11/98 17a- Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
Claims (19)
1. A process for preparing iron oxide yellow pigments in the a-FeOOH modification which comprises a) producing a-FeOOH seeds by precipitation from an Fe(II)-containing solution using an alkaline precipitating agent in the presence of soluble aluminum salts in an amount of 3 to 9 wt.% calculated as A1 2 0 3 with respect to precipitated a-FeOOH, with subsequent oxidation to give a-FeOOH; and b) producing pigment by precipitating further iron with simultaneous oxidation, wherein the seed/time yield is less than 0.3 and the pH over the entire period of pigment growth is less than 3.9; and c) terminating pigment growth at a reproduction factor between 3 and
2. A process according to claim 1, wherein pigment production is terminated at a reproduction factor between 8 and
3. A process according to claim 1, wherein pigment production is terminated at a reproduction factor between 3 and 8.
4. Iron oxide yellow pigments in the a-FeOOH modification with a silking index SI of less than 5, whose color indices on the CIELAB color coordinates in the pure shade and with a pigment/volume concentration of 10 in the test lacquer are a* between 8 and 14, b* between 48.5 and 52 and L* between 54 and 62. Le A 32 688-Foreign Countries -19- Iron oxide yellow pigments according to claim 4, wherein the silking index SI is less than 3.
6. Iron oxide yellow pigments according to claim 4, wherein the silking index SI is less than 1.
7. Iron oxide yellow pigments in the ac-FeOOH modification with a silking index of SI less than 5, whose color indices on the CIELAB color coordinates during lightening with a titanium dioxide pigment at a ratio of 1:5 and with a pigment/volume concentration of 10 in the test lacquer are a* between 3 and 7 and b* between 38 and 41.
8. Iron oxide yellow pigments according to claim 7, wherein the silking index SI is less than 3.
9. Iron oxide yellow pigments according to claim 7, wherein silking index SI is less than 1. Iron oxide yellow pigments produced by the process of claim 1.
11. Iron oxide yellow pigments produced by the process of claim 2.
12. Iron oxide yellow pigments produced by the process of claim 3.
13. A lacquer, paint or plastic material, colored with the iron oxide yellow pigments of claim 4.
14. A lacquer, paint or plastic material colored with the iron oxide yellow pigments of claim -13/11/98 A lacquer, paint or plastic material colored with the iron oxide pigments of claim 6.
16. A lacquer, paint or plastic material colored with the iron oxide yellow pigments of claim 7.
17. A lacquer, paint or plastic material colored with the iron oxide yellow pigments of claim 8.
18. A lacquer, paint or plastic material colored with the iron oxide yellow pigments of claim 9.
19. A lacquer, paint or plastic material colored with the iron oxide yellow pigments of claim
20. A lacquer, paint or plastic material colored with the iron oxide yellow pigments of claim 11.
21. Iron oxide pigments according to any claims 4 to 12, and lacquers containing the same substantially as herein before described with reference to the Examples.
22. A process for the preparation of iron oxide pigments according to claim 1, substantially as hereinbefore described with reference to the Examples. DATED this 12th day of November 1998 BAYER AKTIENGESELLSCHAFT By its Patent Attorneys DAVIES COLLISON CAVE
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1997151141 DE19751141A1 (en) | 1997-11-19 | 1997-11-19 | Non-silk iron oxide yellow pigments with high color |
| DE19751141 | 1997-11-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU9238998A true AU9238998A (en) | 1999-06-10 |
| AU732904B2 AU732904B2 (en) | 2001-05-03 |
Family
ID=7849127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU92389/98A Ceased AU732904B2 (en) | 1997-11-19 | 1998-11-13 | Non-silking iron oxide yellow pigments with high colour density |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6053972A (en) |
| EP (1) | EP0918076B1 (en) |
| JP (1) | JP4359353B2 (en) |
| AU (1) | AU732904B2 (en) |
| BR (1) | BR9804678A (en) |
| DE (2) | DE19751141A1 (en) |
| ES (1) | ES2217480T3 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2421245A1 (en) * | 2000-09-07 | 2003-03-04 | Bayer Aktiengesellschaft | Method for producing an iron oxide nucleus containing aluminium |
| DE10044097A1 (en) * | 2000-09-07 | 2002-04-04 | Bayer Ag | Process for producing an iron oxide seed containing aluminum |
| DK1512726T3 (en) * | 2003-09-03 | 2016-01-18 | Lanxess Deutschland Gmbh | PROCEDURE FOR THE MANUFACTURE OF IRON OXID YELLOW PIGMENTS WITH CACO3 AS A PREPARING AGENT |
| US7237369B2 (en) * | 2003-10-03 | 2007-07-03 | Tipper Tie, Inc. | Automated clipping packaging systems |
| JP2006008935A (en) * | 2004-06-29 | 2006-01-12 | Nippon Paint Co Ltd | Colored coating composition and method for making colored coated film |
| DE102006022449A1 (en) * | 2006-05-13 | 2007-11-15 | Lanxess Deutschland Gmbh | Improved iron oxide yellow pigments |
| JP5101892B2 (en) * | 2007-01-10 | 2012-12-19 | 日本ペイント株式会社 | Colored paint composition and colored coating film |
| US8416477B2 (en) * | 2008-08-08 | 2013-04-09 | Xerox Corporation | Black calibration system and methods for document scanners |
| CN105670345B (en) * | 2016-01-05 | 2017-12-22 | 萧县金鹭纺织品有限公司 | A kind of fire-retardant Method for preparing medium-temperature-rirontant irontant oxide yellow pigment |
| CN113104901B (en) * | 2021-04-13 | 2024-02-09 | 江西理工大学 | Method for preparing iron oxide yellow from rare earth waste acid leaching slag |
| CN113834769A (en) * | 2021-09-03 | 2021-12-24 | 广州天韵达新材料科技有限公司 | Rapid evaluation method for stabilization degree of weather-resistant steel rust layer |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3326632A1 (en) * | 1983-07-23 | 1985-02-07 | Bayer Ag, 5090 Leverkusen | NEW IRON OXIDE YELLOW PIGMENTS WITH LOW SILKING EFFECT AND THEIR PRODUCTION |
| DE3716300A1 (en) * | 1987-05-15 | 1988-11-24 | Bayer Ag | NEW COLOR-PURE IRON OXIDE PIGMENTS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DE3907917A1 (en) * | 1989-03-11 | 1990-09-13 | Bayer Ag | METHOD FOR PRODUCING IRON OXIDE YELLOW PIGMENTS |
| JPH0446019A (en) * | 1990-06-11 | 1992-02-17 | Sumitomo Chem Co Ltd | Production of yellow iron hydroxide pigment |
| DE4434972A1 (en) * | 1994-09-30 | 1996-04-04 | Bayer Ag | Highly transparent, yellow iron oxide pigments, process for their preparation and their use |
| DE4434973A1 (en) * | 1994-09-30 | 1996-04-04 | Bayer Ag | Highly transparent yellow iron oxide pigments, process for their preparation and their use |
-
1997
- 1997-11-19 DE DE1997151141 patent/DE19751141A1/en not_active Withdrawn
-
1998
- 1998-11-11 EP EP19980121458 patent/EP0918076B1/en not_active Expired - Lifetime
- 1998-11-11 DE DE59810895T patent/DE59810895D1/en not_active Expired - Lifetime
- 1998-11-11 ES ES98121458T patent/ES2217480T3/en not_active Expired - Lifetime
- 1998-11-13 AU AU92389/98A patent/AU732904B2/en not_active Ceased
- 1998-11-16 US US09/192,632 patent/US6053972A/en not_active Expired - Lifetime
- 1998-11-18 BR BR9804678A patent/BR9804678A/en not_active IP Right Cessation
- 1998-11-18 JP JP32823498A patent/JP4359353B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0918076A3 (en) | 1999-10-13 |
| EP0918076A2 (en) | 1999-05-26 |
| DE59810895D1 (en) | 2004-04-08 |
| EP0918076B1 (en) | 2004-03-03 |
| AU732904B2 (en) | 2001-05-03 |
| ES2217480T3 (en) | 2004-11-01 |
| DE19751141A1 (en) | 1999-05-20 |
| JPH11240723A (en) | 1999-09-07 |
| JP4359353B2 (en) | 2009-11-04 |
| US6053972A (en) | 2000-04-25 |
| BR9804678A (en) | 1999-11-03 |
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